Process for the production of polyester silicate resinous products

ABSTRACT

By mixing and reacting an alkali metal silicate, a substituted monohydroxy organic compound and a polycarboxylic acid and/or polycarboxylic acid anhydride, polyester silicate resinous products are produced which may be utilized as molding powder, coating agent, etc.

CROSS-REFERENCE TO RELATED COPENDING APPLICATIONS

This application is a continuation-in-part of U.S. patent application,Ser. No. 122,015, filed Feb. 19, 1980, which is a continuation-in-partof U.S. patent application, Ser. No. 10,061, filed Feb. 7, 1979, nowU.S. Pat. No. 4,200,697 which is a continuation-in-part of U.S. patentapplication, Ser. No. 794,915, filed May 9, 1977, now U.S. Pat. No.4,125,498, which is a continuation-in-part of U.S. patent application,Ser. No. 653,727, filed Jan. 30, 1976, now abandoned, which is acontinuation-in-part of U.S. patent application, Ser. No. 562,201, filedApr. 14, 1975, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a process for the production of polyestersilicate resinous products by chemically reacting an alkali metalsilicate, a substituted monohydroxy organic compound and apolycarboxylic acid and/or polycarboxylic acid anhydride by heating themixture to a temperature just below the boiling temperature of thereactants.

The polyester silicate resinous products may be utilized as protectivecoating for wood, metal, plastics, linoleum, leather, fabrics andrubber. They may be utilized in paints, lacquers, metal primers,caulking compounds and water-emulsion paints. They may be copolymerizedwith a vinyl monomer to produce hard, solid, useful objects or they maybe used in conjunction with a reinforcing filler such as fiberglasfiber, paper or cloth to produce a laminate of outstanding strength anddurability which may be used as a molding powder, as an adhesive and asimpregnants. They may be chemically reacted with polyisocyanates toproduce polyurethane silicate resins and foams which may be used forthermal and sound insulation. They may also be reacted withepihalohydrins to produce epoxy silicate resins which may be cured withpolyamines and used as adhesives, coating agents, etc.

The alkali metal silicates will react chemically with the monohydroxyorganic compound, having a substituent which will split off during thereaction, and will react also with the polycarboxylic acid compounds.The unsaturated polyester silicates may be cured with a peroxideinitiator.

Polyester silicate resinous products may be produced by reacting thefollowing components:

(A) an alkali metal silicate;

(B) an organic monohydroxy compound having a substituent which willsplit off during the reaction;

(C) a polycarboxylic acid and/or a polycarboxylic acid anhydride.

Component A

Any suitable alkali metal silicate may be used in this invention, suchas sodium silicate, potassium silicate, lithium silicate and mixturesthereof.

Sodium silicate is the preferred alkali metal silicate. An aqueoussolution of alkali metal silicate may be used, but a fine granularalkali metal silicate is preferred.

Component B

Any suitable organic monohydroxy compound having a substituent whichwill split off during the reaction. The substituent can be halogen, acidsulfate, nitrate, acid phosphate, bicarbonate, sulfate, formate,acetate, propionate, laurate, oleate, stearate, and mixtures thereof.

The halohydrins are the preferred organic monohydroxy-substitutedcompound. Suitable halohydrins include the alkene halohydrins such asethylene chlorohydrin, ethylene bromohydrin, glycerine α,γdichlorohydrin and the like.

Aliphatic nitro alcohols are produced by reacting nitroalkanes withaldehydes or ketones in the presence of dilute alkali to producecompounds with the general formula of ##STR1## wherein R is an alkane.2-nitro-1-hydroxy alkane compounds may be used. Nitro-phenols may beused.

Component C

The polycarboxylic acid may be aliphatic, cycloaliphatic, aromaticand/or heterocyclic and may be substituted, e.g., with halogen atoms andmay be unsaturated; examples include: succinic acid, adipic acid,sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalic acidanhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, fumaric acid, maleicacid, dimethylterephthalate and bis-glycol terephthalate.

Long-chain unsaturated alkali metal polyester silicate resins may bemade from dibasic acids and dihydric alcohols. Either the dibasic acidor the dihydric alcohol may be unsaturated. Usually a combination ofunsaturated and saturated dibasic acids and dihydric alcohols is used toproduce the unsaturated polyester resins. Instead of the dibasic acids,the corresponding polycarboxylic acid esters of lower alcohols or theirmixtures e.g. dimethylterephthalate and bis-glycol terephthalate, may beused for preparing the unsaturated polyester resins.

Suitable dibasic acids may be aliphatic, cycloaliphatic, aromatic and/orheterocyclic and may be substituted, e.g., with halogen atoms. Examplesof the dibasic acid and corresponding acid anhydride include, but arenot limited to, succinic acid, adipic acid, suberic acid, azelaic acid,phthalic acid, sebacic acid, isophthalic acid, trimellitic acid,phthalic acid anhydride, tetrahydrophthalic acid anhydride,hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acidanhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride,fumaric acid. An unsaturated dibasic acid such as maleic acid, maleicacid anhydride, fumaric acid, itaconic acid or mixtures thereof must beincluded in the production of unsaturated alkali metal polyestersilicate resins, except when an unsaturated alcohol is used.

A portion, up to 5 parts by weight, of the polycarboxylic acid and/orpolycarboxylic acid anhydride may be replaced by polymerizable oils suchas unsaturated fatty acids (or their esters), tung oil, linseed oil,heated linseed oil, soybean oil, dehydrated castor oil, tall oil,cottonseed oil, sunflower oil, fish oil, perilla oil, safflower oil andmixtures thereof. 10 to 30 parts by weight of polycarboxylic acid and/orpolycarboxylic anhydride are used in this invention.

A portion, up to 5 parts by weight, of the polycarboxylic acid and/orpolycarboxylic acid anhydride may be replaced with a linear organiccarbonate selected from the group consisting of p-xylene glycolbis(ethyl carbonate), diethylene glycol bis(allyl carbonate) andmixtures thereof.

A portion, up to 5 parts by weight, of the substituted organicmonohydroxy compound and polycarboxylic acid is replaced with an organiccompound containing hydroxyl and carboxylic radicals, selected from thegroup consisting of 10-hydroxy undecanoic acid, 2-hydroxy decanoic acid,W-hydroxy pentadecanoic acid and mixtures thereof.

Any suitable polymerizing monomer may be used with the unsaturatedpolyester resin such as, but not limited to, vinyl monomers, allylesters, triallyl cyanurate and mixtures thereof.

Styrene is the preferred polymerizing monomer and may be used alone orin combination with vinyl acetate. Other vinyl monomers may be used suchas acrylic acid compounds and esters, vinyl toluene, divinyl benzene,acrylonitrile, methacrylonitrile, etc. The vinyl monomer may be added inan amount of 20 to 50 percent by weight, percentage based on the weightof the polyester silicate resinous product.

Activators and promoters, used in conjunction with the initiators suchas cobalt which, in the form of its ethyl hexanoate or naphthenate salt,is a good, general-purpose activator for use with ketone peroxides, maybe added to the unsaturated polyester resin. Concentration as low as 30ppm of cobalt metal will activate a system. Other activators may beadded to the unsaturated polyester resins such as tertiary dialkyl arylamines, e.g., diethyl aniline, and aliphatic thiols, e.g., laurylmercaptan, when acyl peroxides are used. When alkali metal or ammoniumpersulfates are used, ferric sulfate and cupric sulfate may be added tothe unsaturated polyester resin.

An inhibitor, such as p-tert-butyl catechol, hydroquinone, p-nitrosedimethylaniline or similar compounds which will increase the lifetime ofthe unsaturated polyester resin, may be added to the unsaturatedpolyester resin.

Any suitable initiator which will promote the copolymerization of asolution of an unsaturated linear polymer in a liquid monomer may beused in this invention. The controlled polymerization of unsaturatedpolyester-monomer mixture, in order to yield fully cured solids, usuallyrequires the use of an initiator.

Any suitable free-radical initiator, such as organic and inorganicperoxides, azo compounds, alkali metal persulfates, ammonium persulfateand mixtures thereof, may be used. The fact that the action of organicperoxide can be modified by activators and promoters, plus their readyavailability at reasonable cost, makes them preferable in thisinvention. Thermal and photopolymerization may be used in certain cases.

Suitable organic peroxide initiators include, but are not limited to,acetyl benzoyl peroxide, peracetic acid, methyl ethyl ketone peroxide,cyclohexanone peroxide, cyclohexyl hydroperoxide, 2,4-dichlorobenzoylperoxide, cumene hydroperoxide, tert-butyl hypoperoxide, methyl amylketone peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperbenzoate, di-tert-butyl diperphthalate and mixtures thereof. Theamount of organic peroxide needed to promote the catalytic reaction isquite varied; usually less than 1%, based on the weight of thereactants, is needed. Methyl ethyl ketone peroxide is added in an amountof 0.2 to 0.1% by weight, based on the polyester silicate resinousproduct.

Promoters used with acyl peroxide include tertiary dialkyl aryl amines,such as diethyl aniline, and aliphatic thiols like, for example, laurylmercaptan. Concentrations used are most often in the range of 0.05% to0.5% of active substance. Promoters usually are strong reducing agentsand initiators are strong oxidizing agents.

Suitable alkali metal persulfates include potassium and sodiumpersulfate. Redox systems may also be utilized in this invention(activation of initiators by a reducing agent).

The alkali metal polyester silicate resinous product will reactchemically with suitable polyisocyanates and/or polyisothiocyanates toproduce resinous products and foams.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromaticand heterocyclic polyisocyanates and mixtures thereof. Suitablepolyisocyanates which may be employed in the process of the inventionare exemplified by the organic diisocyanates which are compounds of thegeneral formula

    O═C═N--R--N═C═O

where R is a divalent organic radical such as an alkylene, aralkylene orarylene radical. Such suitable radicals may contain, for example, 2 to20 carbon atoms. Examples of such diisocyanates are:

tolylene diisocyanate,

p,p'-diphenylmethane diisocyanate (sic),

phenylene diisocyanate,

m-xylylene diisocyanate,

chlorophenylene diisocyanate,

benzidene diisocyanate,

naphthylene diisocyanate,

decamethylene diisocyanate,

hexamethylene diisocyanate,

pentamethylene diisocyanate,

tetramethylene diisocyanate,

thiodipropyl diisocyanate,

propylene diisocyanate, and

ethylene diisocyanate.

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates are also suitable and have thegeneral formula ##STR2## where x+y totals 6 to 22 and x is 0 to 2, e.g.,isocyanastearyl isocyanate.

It is generally preferred to use commercially readily availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers ("TDI"), polyphenylpolymethylene-isocyanatesobtained by aniline-formaldehyde condensation followed by phosgenation("crude MDI"), and modified polyisocyanate containing carbodiimidegroups, isocyanurate groups, urea groups, imide groups, amide groups orbiuret groups, said modified polyisocyanates prepared by modifyingorganic polyisocyanates thermally or catalytically by air, water,urethanes, alcohols, amides, amines, carboxylic acids, or carboxylicacid anhydrides, phosgenation products of condensates of aniline oranilines alkylsubstituted on the nucleus, with aldehydes or ketones maybe used in this invention. Solutions of distillation residuesaccumulating during the production of tolylene diisocyanates, diphenylmethane diisocyanate, or hexamethylene diisocyanate, in monomericpolyisocyanates or in organic solvents or mixtures thereof may be usedin this invention. Organic triisocyanates such as triphenylmethanetriisocyanate may be used in this invention. Cycloaliphaticpolyisocyanates, e.g., cyclohexylene-1,2-; cyclohexylene-1,4; andmethylene-bis-(cyclohexyl-4,4') diisocyanate may be used in thisinvention. Suitable polyisocyanates which may be used according to theinvention are described, e.g., by W. Siefkin in Justus Liebigs Annalender Chemie, 562, pages 75 to 136. Inorganic polyisocyanates are alsosuitable according to the invention.

Organic polyhydroxyl compounds (polyols) may be used in this inventionwith polyisocyanates or may be first reacted with a polyisocyanate toproduce isocyanate-terminated polyurethaneprepolymers and then also usedin this invention.

Reaction products of from 50 to 99 mols of aromatic diisocyanates withfrom 1 to 50 mols of conventional organic compounds with a molecularweight of, generally, from about 200 to about 10,000 which contain atleast two hydrogen atoms capable of reacting with isocyanates, may alsobe used. While compounds which contain amino groups, thiol groups,carboxyl groups or silicate groups may be used, it is preferred to useorganic polyhydroxyl compounds, in particular, compounds which containfrom 2 to 8 hydroxyl groups, especially those with a molecular weight offrom about 800 to about 10,000 and preferably from about 1,000 to about6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates or polyester amides containing at least 2, generally from2 to 8, but preferably dihydric alcohols, with the optional addition oftrihydric alcohols, and polybasic, preferably dibasic, carboxylic acids.Instead of the free polycarboxylic acids, the correspondingpolycarboxylic acid anhydrides or corresponding polycarboxylic acidesters of lower alcohols or their mixtures may be used for preparing thepolyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic,aromatic and/or heterocyclic and may be substituted, e.g., with halogenatoms and may be unsaturated; examples include: succinic acid, adipicacid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalicacid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbis-glycol terephthalate. Any suitable polyhydric alcohol may be usedsuch as, for example, ethylene glycol; propylene-1,2- and -1,3-glycol;butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol;neopentyl glycol, cyclohexanedimethanol(1,4-bis-hydroxymethylcyclohexane); 2-methylpropane-1,3-diol; glycerol;trimethylol propane; hexane-1,2,6-triol; butane-1,2,4-triol; trimethylolethane; pentaerythritol; quinitol; mannitol and sorbitol;methylglycoside; diethylene glycol; triethylene glycol; tetraethyleneglycol; polyethylene glycols; dipropylene glycol; polypropylene glycols;dibutylene glycol and polybutylene glycols. The polyesters may alsocontain a proportion of carboxyl end groups. Polyesters of lactones,such as c-caprolactone, or hydroxycarboxylic acid such asω-hydroxycaproic acid, may also be used.

The polyethers with at least 2, generally from 2 to 8 and preferably 2or 3, hydroxyl groups used according to the invention are known and maybe prepared, e.g., by the polymerization of epoxides, e.g., ethyleneoxide, propylene oxide, butylene oxide, tetrahydrofurane oxide, styreneoxide or epichlorohydrin, each with itself, e.g., in the presence ofBF₃, or by addition of these epoxides, optionally as mixtures orsuccessively, to starting components which contain reactive hydrogenatoms such as alcohols or amines, e.g., water, ethylene glycol;propylene-1,3- or -1,2-glycol; trimethylol propane;4,4-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine orethylenediamine; sucrose polyethers such as those described, e.g., inGerman Auslegeschriften Nos. 1,176,358 and 1,064,938 may also be usedaccording to the invention. It is frequently preferred to use polyetherswhich contain predominantly primarily OH groups (up to 90% by weight,based on the total OH groups contained in the polyether). Polyethersmodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitriles in the presence of polyethers(U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695; andGerman Pat. No. 1,152,536) and polybutadienes which contain OH groupsare also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythio-mixed ethers or polythioether esteramides, depending on the co-component.

The polyacetals used may be, for example, the compounds which may beobtained from glycols, 4,4'-dihydroxydiphenylmethylmethane, hexanediol,and formaldehyde. Polyacetals suitable for the invention may also beprepared by the polymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the kind, e.g.,which may be prepared by reaction diols, e.g., propane-1,3-diol;butane-1,4-diol; and/or hexane-1,6-diol or diethylene glycol,triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonates or phosgene.

The polyester amides and polyamides include, e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides, any polyvalent saturated orunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxyl compounds which contain urethane or urea groups, modifiedor unmodified natural polyols, e.g., castor oil, carbohydrates andstarches, may also be used. Additional products of alkylene oxides withphenol formaldehyde resins or with urea-formaldehyde resins are alsosuitable for the purpose of the invention.

Organic hydroxyl silicate compound as produced in U.S. Pat. No.4,139,549 may also be used in this invention.

Examples of these compounds which are to be used according to theinvention have been described in High Polymers, Volume XVI,"Polyurethanes, Chemistry and Technology", published by Saunders-FrischInterscience Publishers, New York, London, Volume I, 1962, pages 32 to42 and pages 44 to 54, and Volume II, 1964, pages 5 and 16 and pages 198and 199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen-Verlag,Munich, 1966, on pages 45 to 71.

If the polyisocyanates or the prepolymer which contains NCO groups havea viscosity above 2000 cP at 25° C., it may be advantageous to reducethe viscosity thereof by mixing it with a low-viscosity organicpolyisocyanate and/or an inert blowing agent or solvent.

Inorganic polyisocyanates and isocyanate-terminated polyurethanesilicate prepolymers may also be used in this invention.

Polyisocyanate curing agents and/or polyisocyanate activators(catalysts) may be used in the process of producing poly(urethanesilicate) resinous or foamed products. The following are examples ofpolyisocyanate curing agents and activators:

1. Water.

2. Water containing 10% to 70% by weight of an alkali metal silicate,such as sodium and/or potassium silicate. Crude commercial alkali metalsilicate may contain other substances, e.g., calcium silicate, magnesiumsilicate, borates or aluminates and may also be used. The molar ratio ofMe₂ OSiO₂ (Me=alkali metal) is not critical and may vary within theusual limits, but is preferably between between 4 to 1 and 0.2 to 1.

3. Water containing 20% to 50% by weight of ammonium silicate.

4. Water containing 5% to 40% by weight of magnesium oxide in the formof a colloidal dispersion.

5. Alkali meta metasilicate such as sodium metasilicate, potassiummetasilicate and commercial dry granular sodium and potassium silicates.Heating is required to start the curing reaction.

6. Water containing 20% to 70% by weight of silica sol.

7. Activators (catalysts) which act as curing agents and are added tothe polyurethane silicate prepolymer in the amount of 0.001% to 10% byweight. They may be added in water.

(a) Tertiary amines, e.g., triethylamine; tributylamine;N-methyl-morpholine; N-ethylmorpholine; N,N,N',N'-tetramethylenediamine;1,4-diazo-bicyclo-(2,2,2)-octane; N-methyl-N'-dimethylaminoethylpiperazine; N,N-dimethylbenzylamine; bis(N,N-diethylaminoethyl)-adipate;N,N-diethylbenzylamine; pentamethyldiethylenetriamine;N,N-dimethylcyclohexylamine; N,N,N',N'-tetramethyl-1,3-butanediamine;N,N-dimethyl-beta-phenylethylamine; and 1,2-dimethylimidazole. Suitabletertiary amine activators which contain hydrogen atoms which arereactive with isocyanate groups include, e.g., triethanolamine;triisopanolamine; N,N-dimethylethanolamine; N-methyl-diethanolamine;N-ethyl-diethanolamine; and their reactive products with alkyleneoxides, e.g., propylene oxide and/or ethylene oxide and mixturesthereof.

(b) Organo-metallic compounds, preferably organo-tin compounds such astin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethylhexoate, and tin laurate and the dialkyl tin salts of carboxylic acids,e.g., dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleateor diocyl tin diacetate.

(c) Silaamines with carbon-silicon bonds as described, e.g., in BritishPat. No. 1,090,589, may also be used as activators, e.g.,2,2,4-trimethyl-1,2-silamorpholine or1,3-diethylaminoethyl-tetramethyldisiloxane.

(d) Other examples of catalysts which may be used according to theinvention, and details of their action, are described inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hander-Verlag, Munich, 1966, e.g., on pages 96 and 102.

8. Water containing 1% to 10% by weight of bases which contain nitrogensuch as tetraalkyl ammonium hydroxides.

9. Water containing 1% to 10% by weight of alkali metal hydroxides suchas sodium hydroxide; alkali metal phenolates such as sodium phenolate oralkali metal alcoholates such as sodium methylate.

10. Water containing sodium polysulfide in the amount of 1% to 10% byweight.

11. Water containing 20% to 70% by weight of a water-binding agent,being capable of absorbing water to form a solid or a gel, such ashydraulic cement, synthetic anhydrite, gypsum or burnt lime.

12. Mixtures of the above curing agents.

Surface-active additives (emulsifiers and foam stabilizers) may also beused according to the invention. Suitable emulsifiers are, e.g., thesodium salts of ricinoleic sulphonates or of fatty acid, or salts offatty acids with amines, e.g., oleic acid diethylamine or stearic aciddiethanolamine. Other surface-active additives are alkali metal orammonium salts of sulphonic acids, e.g., dodecylbenzine sulphonic acidor dinaphthyl methane disulphonic acid; or of fatty acids, e.g.,ricinoleic acid, or of polymeric fatty acids.

The form stabilizers used are mainly water-soluble polyester siloxanes.These compounds generally have a polydimethylsiloxane group attached toa copolymer of ethylene oxide and propylene oxide. Foam stabilizers ofthis kind have been described, e.g., in U.S. Pat. No. 3,629,308. Theseadditives are preferably used in quantities of 0% to 20%, but preferably0.01% to 20%, by weight, based on the reaction mixture.

Negative catalysts, for example, substances which are acidic inreaction, e.g., hydrochloric acid or organic acid halides, known cellregulators, e.g., paraffins, fatty alcohols or dimethyl polysiloxanes,pigments or dyes, known flame-retarding agents, e.g.,tris-chloroethylphosphate or ammonium phosphate and polyphosphates,stabilizers against aging and weathering plasticizers, fungicidal andbacteriocidal substances and fillers, e.g., barium sulphate, kieselguhr,carbon black or whiting, may also be used according to the invention.

Further examples of surface additives, foam stabilizers, cellregulators, negative catalysts, stabilizers, flame-retarding substances,plasticizers, dyes, fillers and fungicidal and bacteriocidal substancesand details about methods of using these additives and their action maybe found in Kunststoff-Handbuch, Volume VI, published by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 103 to 113.The halogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retarding agents.

The preferred curing agent is an aqueous solution of silicates, sodiumsilicate and/or potassium silicate in water, which are normally known aswater glass. Aqueous solutions of silicates may be prepared in the formof 25% to 54% silicates. Silica sols which may have an alkaline or acidpH may also be used; they should have solid contents of 15% to 50%.Silica sols are generally used in combination with aqueous silicatesolutions. The choice of concentration depends mainly on the desired endproduct. Compact materials or materials with closed cells are preferablyproduced with concentrated silicated solutions which, if necessary, areadjusted to a lower viscosity by addition of alkali metal hydroxide.Solutions with concentrations of 40% to 70% by weight can be prepared inthis way. On the other hand, to produce open-celled, light-weight foams,it is preferred to use silicate solutions with concentrations of 20% to45% by weight in order to obtain low viscosities, sufficiently longreaction times and low unit weights. Silicate solutions withconcentrations of 15% to 45% are also preferred when substantialquantities of finely divided inorganic fillers are used.

Suitable flame-resistant compounds may be used in the products of thisinvention such as those which contain halogen or phosphorous, e.g.,tributylphosphate; tris(2,3-dichloropropyl)-phosphate;polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate;tricresylphosphate; tris-(betachloroethyl)-phosphate;tris-(2,3-dichloropropyl)-phosphate; triphenyl-phosphate; ammoniumphosphate; perchlorinated diphenyl phosphate; perchlorinated terephenylphosphate; hexabromocyclodecane; tribromophenyl; dibromopropyldiene;hexabromobenzene; octabromodiphenylether; pentabromotoluol;poly-tribromostyrol; tris-(bromocresyl)-phosphate; tetrabromobisphenolA; tetrabromophthalic acid anhydride; octabromodiphenyl phosphate;tri-(dibromopropyl)-phosphate; calcium hydrogen phosphate; sodium orpotassium dihydrogen phosphate; disodium or dipotassium hydrogenphosphate; ammonium chloride; phosphoric acid; polyvinylchloridetetomers chloroparaffins as well as further phosphorus- and/orhalogen-containing flame-resistant compounds as they are described inKunststoff-Handbuch, Volume VII, Munich, 1966, pages 110 and 111, whichare incorporated herein by reference. The organic halogen-containingcomponents are, however, preferred in the polyurethane silicateproducts.

The object of the present invention is to provide a novel process toproduce polyester silicate resinous products. Another object is toproduce polyester silicate resinous products which will react with anepihalohydrin compound to produce epoxy silicate resinous products. Afurther object is to produce polyester silicate resinous products whichwill react with polyisocyanates to produce resinous and foamed productsthat may be used as coating agents and thermal- and sound-insulationmaterials. Another object is to produce polyurethane silicate foamedproducts which have excellent flame-retardant properties.

DETAILED DESCRIPTION OF THE INVENTION

I have discovered that a polyester silicate resinous product may beproduced by reacting an alkali metal silicate, a substituted monohydroxyorganic compound and a polycarboxylic acid and/or a polycarboxylic acidanhydride.

The preferred method is to mix, simultaneously, Component A, an alkalimetal silicate, Component B, a substituted monohydroxy organic, andComponent C, a polycarboxylic acid and/or a polycarboxylic acidanhydride, then to heat the mixture to a temperature between the meltingtemperature of the polycarboxylic acid and the boiling temperature ofthe components while agitating for 20 to 90 minutes, thereby producing apolyester silicate resinous product.

The exact chemical reaction which takes place is not known, but appearsto be as follows: ##STR3## The polycarboxyl compound appears to act as acatalyst to promote the reaction of the halohydrin with the silicate.

The reactions of this invention may take place under any suitablephysical conditions. While most of the reactions will take place atambient pressure, in certain cases, a pressure either lower than, orabove, ambient pressure may give better results. It may be preferable incertain cases to use temperatures above the components' boilingtemperature after a partial reaction has taken place in order to speedup the chemical reaction. The temperature usually ranges between 100° C.and 250° C.

The ratios of the essential reactants and optional reactants which leadto the polyester silicate resinous product of this invention may vary,broadly speaking, within ranges as follows:

(A) 1 to 10 parts by weight of alkali metal;

(B) 10 to 30 parts by weight of a monohydroxyl organic compound having asubstituent which will split off during the reaction;

(C) 10 to 30 parts by weight of a polycarboxylic acid and/orpolycarboxylic acid anhydride.

Polyester silicates will react chemically with polyisocyanates and/orpolyisothiocyanates to produce a polyurethane silicate resinous productor foam.

The preferred method to produce polyurethane silicate resinous or foamproducts is to mix thoroughly 1 to 95 parts by weight of the polyestersilicate resinous product with 50 parts by weight of a polyisocyanate orpolyisothiocyanate at a temperature between 20° C. and 45° C. and at asuitable pressure, preferably ambient, optionally adding catalyst(activator), foam stabilizers, blowing agent, polyols and fillers. Theoptical additives may be premixed with the suitable component. Theblowing agent may be added with the polyester or polyisocyanate and theremaining additives are added with the polyester silicate resinousproduct.

The polyisocyanate may be reacted with a polyol to produce anisocyanate-terminated polyurethane prepolymer and used in place of, orwith, the polyisocyanate to react with the polyester silicare to producea polyurethane silicate resinous or foamed product.

Water-binding agents may be optionally added with the polyestersilicate, activator and polyisocyanate to produce a rigid foamedpolyurethane silicate product which is then wet with water to cure thewater-binding agent.

The ratios of the essential reactants and optional reactants which leadto the polyurethane silicate resinous or foamed product of thisinvention may vary, broadly speaking, with ranges as follows:

(a) 1 to 95 parts by weight of polyester silicate resinous product;

(b) 50 parts by weight of polyisocyanate, polyisothiocyanate orisocyanate-terminated polyurethane prepolymer;

(c) up to 20% by weight of a foam stabilizer;

(d) up to 50% by weight of a chemically inert blowing agent, boilingwithin the range of from -25° C. to 80° C.;

(e) up to 10% by weight of an activator;

(f) up to 200 parts by weight of a water-binding agent;

(g) up to 100 parts by weight of a curing agent.

Percentages are based on the weight of the alkali metal polyestersilicate resinous product and polyisocyanate.

In the cases where the viscosity of the polyisocyanate is too high, itmay be reduced by adding a low-viscosity isocyanate, or even by addinginert solvents such as acetone, diethyl ether or diethylene glycol,ethyl acetate and the like.

In cases where the curing agent contains an aqueous alkali silicate, theisocyanate-terminated polyurethane prepolymer should be sulphonated. Itis usually sufficient to react the isocyanate-terminated polyurethaneprepolymer with concentrated sulphuric acid or oleum of sulfur trioxidein order to produce a sulphonated poly(urethane silicate) prepolymercontaining the sulphonic group in the amount of 3 to 100milliequivalents/100 g. The reaction will take place by thoroughlymixing the sulphuric acid or oleum or sulfur trioxide with theisocyanate-terminated polyurethane prepolymer at ambient temperature andpressure. In some cases where sulfur trioxide is used, an increasedpressure is advantageous. The polyisocyanate may be modified to containionic groups before reacting with the polyester-silicate resinousproducts.

The sulphonated isocyanate-terminated polyurethane prepolymer can bedirectly mixed with an aqueous silicate solution, in which case thecorresponding metal salt is formed in situ. The sulphonatedpoly(urethane silicate) prepolymer may be completely or partlyneutralized at the onset by the addition of amines, metal alcoholates,metal oxides, metal hydroxide or metal carbonates.

Water-binding components may be used in this invention, includingorganic or inorganic water-binding substances which have, first, theability to chemically combine, preferably irreversibly, with water and,second, the ability to reinforce the poly(urethane silicate) plastics ofthe invention. The term "water-binding component" is used herein toidentify a material, preferably granular or particulate, which issufficiently anhydrous to be capable of absorbing water to form a solidor gel such as mortar or hydraulic cement.

A water-binding component such as hydraulic cement, syntheticanhydrides, gypsum or burnt lime may be added to any of the componentsin the production of polyurethane silicate so as to produce a tough,somewhat flexible solid or cellular solid concrete. The water-bindingcomponent may be added in amounts up to 200% by weight, based on theweight of Components A, B and C. When a water-binding agent is added andwhen the curing agent is an aqueous alkali metal silicate solution, ahalogen or phosphorous-containing compound or mixture thereof may beadded in the amount of 1% to 30% by weight, based on the weight of thereactants.

Suitable hydraulic cements are, in particular, Portland cement,quick-setting cement, blast-furnace Portland cement, mild-burnt cement,sulphate-resistant cement, brick cement, natural cement, lime cement,gypsum cement, pozzolan cement and calcium sulphate cement. In general,any mixture of fine ground lime, alumina and silica that will set to ahard product by admixture of water, which combines chemically with theother ingredients to form a hydrate, may be used. There are many kindsof cement which can be used in the production of the compositions of theinvention and they are so well known that a detailed description ofcement will not be given here; however, one can find such a detaileddescription in Encyclopedia of Chemical Technology, Volume 4, SecondEdition, Published by Kirk-Othmer, pages 684 to 710, of the type ofcement which may used in the production of this invention and thisdescription is incorporated herein by reference. Up to 300% by weight ofa water-binding agent may be used with the unsaturated polyestersilicate vinyl monomer, water up to 30% by weight based on thewater-binding agent, and a peroxide initiator.

Organic blowing agents may be used to improve or increase the foaming toproduce cellular solid plastics such as acetone, ethyl acetate,methanol, ethanol, halogenated alkanes, e.g., methylene chloride,chloroform, ethylidene chloride, vinylidene chloride,monofluorotrichloromethane, chlorodifluoromethane, butane, hexane ordiethyl ether. Compounds which decompose at temperatures above roomtemperature with liberation of gases, e.g., nitrogen, such as azocompounds, azoisobutyric acid nitrile, may also act as blowing agents.Compressed air may act as a blowing agent. Other examples of blowingagents and details about the use of blowing agents are described inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 108 and 109, 453 to 455and 507 to 510.

The proportions of the components may be adjusted to a highly cellularsolid. When water is used, it reacts with the NCO group to produce CO₂and pores are produced in the product by the evolved CO₂. In certaincases, the CO₂ is rapidly evolved and escapes before the producthardens, and a solid product can be produced, nearly completely free ofair cells. When a high silicate content, from 80% to 99% by weight, isdesirable, such as when the final product is required to have mainly theproperties of an inorganic silicate plastic, in particular,high-temperature resistance and complete flame resistance, an alkalimetal silicate may be added with the components to be reacted with thepolyisocyanate to produce a poly(urethane alkali silicate) prepolymer.In that case, the function of the polyisocyanate is that of anon-volatile hardener whose reaction product is a high-molecular-weightpolymer which reduces the brittleness of the product.

When an alkali catalyst or alkali metal silicate is used in theinvention, fine metal powders, e.g., powdered calcium, magnesium,aluminum or zinc, may also act as the blowing agents by bringing aboutthe evolution of hydrogen. Compresed air may be mixed in the componentsand may also be used to mix the components, then be used as the blowingagent. These metal powders also have a hardening and reinforcing effect.

The properties of the foams (cellular solid) obtained from any givenformulation, e.g., their density in the moist state, depends to someextent on the details of the mixing process, e.g., the form and speed ofthe stirrer and the form of the mixing chamber, and also the selectedtemperature at which foaming is started. The foams will usually expand 3to 12 times their original volume.

The poly(urethane silicate) plastics produced by the invention have manyuses. The reaction mixture, with or without a blowing agent, may bemixed in a mixing apparatus; then the reaction mixture may be sprayed bymeans of compressed air or by the airless spraying process ontosurfaces; subsequently, the mixture expands and hardens in the form of acellular solid which is useful for insulation, filling, andmoisture-proofing coating. The foaming material may also be forced,poured or injection-molded into cold or heated molds, which may berelief molds or solid or hollow molds, optionally by centrifugalcasting, and left to harden at room temperature or at temperatures up to200° C., at ambient pressure or at elevated pressure. In certain cases,it may be necessary to heat the mixing or spraying apparatus to initiatefoaming; then, once foaming has started, the heat evolved by thereaction between components continues the foaming until the reaction iscomplete. A temperature between 40° C. and 150° C. may be required toinitiate foaming. The blowing agent may be added to the polyisocyanate.

Reinforcing elements may quite easily be incorporated into the reactionmixtures. The inorganic and/or organic reinforcing elements may be e.g.,fibers, metal wires, foams, fabrics, fleeces or skeletons. Thereinforcing elements may be mixed with the reaction mixtures, forexample, by the fibrous web impregnation or by processes in which thereaction mixtures and reinforcing fibers are together applied to themold, for example, by means of a spray apparatus. The shaped productsobtainable in this way may be used as building elements, e.g., in theform of sandwich elements, either as such or after they have beenlaminated with metal, glass or plastics; if desired, these sandwichelements may be foamed. The products may be used as hollow bodies, e.g.,as containers for goods which may be required to be kept moist or cool,as filter materials or exchanges, as catalyst carriers or carriers ofother active substances, as decorative elements, furniture componentsand fillings or for cavities. They may be used in the field of modelbuilding and mold building, and the production of molds for metalcasting may also be considered.

Instead of blowing agents, finely divided inorganic or organic hollowparticles, e.g., hollow expanded beads of glass, plastics and straw, maybe used for producing cellular solid products. These products may beused as insulating materials, cavity fillings, packaging materials,building materials which have good solvent resistance and advantageousfire-resistant characteristics. They may also be used as lightweightbuilding bricks in the form of sandwiches, e.g., with metalcoveringlayers for house building and the construction of motor vehicles andaircraft.

Organic or inorganic particles which are capable of foaming up or havealready been foamed may be incorporated in the fluid foaming reactionmixture, e.g., expanded clay, expanded glass, wood, cork, popcorn,hollow plastic beads such as beads of vinyl chloride polymers,polyethylene, styrene polymers, or foam particles of these polymers orother polymers, e.g., polysulphone, polyepoxide, polyurethane,poly(urethane silicate) copolymers, urea-formaldehyde,phenol-formaldehyde or polyimide polymers, or, alternatively, heaps ofthese particles may be permeated with foaming reaction mixtures toproduce insulation materials which have good fire-resistantcharacteristics.

The cellular solid products of the invention, in the aqueous or dry orimpregnated state, may subsequently be lacquered, metallized, coated,laminated, galvanized, vapor treated, bonded or blocked. The cellularsolid products may be sawed, drilled, planed, polished, or other workingprocesses may be used to produce shaped products. The shaped products,with or without a filler, may be further modified in their properties bysubsequent heat treatment, oxidation processes, hot pressing, sinteringprocesses or surface melting or other compacting processes.

The novel cellular solid products of the invention are also suitable foruse as constructional materials due to their toughness and stiffness,yet they are still elastic. They are resistant to tension andcompression and have a high-dimensional stability to heat and high flameresistance. They have excellent sound-absorption capacity,heat-insulating capacity, fire resistance and heat resistance, whichmakes them useful for insulation. The cellular products of thisinvention may be foamed on the building site and, in many cases, used inplace of wood or hard fiber boards. Any hollow forms may be used forfoaming. The brittle foams may be crushed and used as a filler, as asoil conditioner, as a substrate for the propagation of seedlings,cuttings and plants or cut flowers.

The foamed or solid concrete produced by reacting polyester silicateresinous product, optionally a blowing agent and initiator, andpolyisocyanate with a water-binding component may be used as surfacecoatings having good adhesion and resistance-to-abrasion properties, asmortars, and for making molded products, particularly in constructionengineering and civil engineering such as for building walls, igloos,boats and for roadbuilding, etc. These products are light-weight,thermal-insulating materials with excellent mechanical properties andfire-resistance. The amount of water-binding component used variesgreatly, depending on the type of product desired, from 1% to 200% byweight, based on Components A, B and C and polyisocyanate. In certaincases, it is desirable to add sand and gravel in the amount of 1 to 6parts by weight to each part by weight of the hydraulic cement. Themixture may be poured in place, troweled on or sprayed onto the desiredsurface to produce a solid or cellular solid product.

Fillers in the form of powders, granules, wire, fibers, dumb-bell-shapedparticles, crystallites, spirals, rods, beads, hollow beads, foamparticles, non-woven webs, pieces of woven or knitted fabrics, tapes andpieces of foil of solid inorganic or organic substances, e.g., dolomite,chalk, alumina, asbestos, basic silicic acids, sand, talc, iron oxides,aluminum oxide and hydroxides, alkali metal silicates, zeolites, mixedsilicates, calcium silicate, calcium sulphates, alumino silicates,cements, basalt wool or powder, glass fibers, carbon fibers, graphite,carbon black, Al, Fe, Cri and Ag powders, molybdenum sulphide, steelwool, bronze or copper meshes, silicon powder, expanded clay particles,hollow glass beads, glass powder, lava and pumice particles, wood chips,woodmeal, cork, cotton, straw, popcorn, coke or particles of filled orunfilled, foamed or unfoamed, stretched or unstretched organic polymers,may be added to the mixture of the Components A, B and C in manyapplications. Among the numerous organic polymers which may be used,e.g., as powders, granules, foam particles, beads, hollow beads,foamable (but not-yet-foamed) particles, fibers, tapes, woven fabrics,or fleeces, the following may be mentioned as examples: polystyrene,polyethylene, polypropylene, polyacrylonitrile, polybutadiene,polyisoprene, polytetrafluorethylene, aliphatic and aromatic polyesters,melamine, urea, phenol resins, phenol silicate resins, polyacetalresins, polyepoxides, polyhydantoins, polyureas, polyethers,polyurethanes, polyimides, polysulphones, polycarbonates and copolymersthereof.

The composite materials, according to the invention, may be mixed withconsiderable quantities of fillers without losing their advantageousproperties, and, in particular, composite materials which consistpredominantly of organic constituents which are preferably filled withinorganic fillers; where silicate constituents predominate, it ispreferably filled with organic fillers. Fillers which are particularlypreferred are chalk, talc, dolomite, gypsum, clay, anhydrite, glass,carbon and the conventional plastics and rubber waste.

In the production of surface coatings, bonds, putties or interlayers,particularly in the case of porous materials, it is preferred to usepolyisocyanates which have only a low isocyanate content, e.g., lessthan 5%, or prepolymers which are free from isocyanate groups. Themixtures obtained in this way have a long pot life and may be applied inthin layers which gradually harden in the course of time. The liberatedCO₂ acts as the curing agent. In a two-stage or multistage hardening inwhich, for example, an excess of water is used, there is a rapidevolution of CO₂ and the poly(urethane silicate) resinous product isconverted into a workable form which may be used as putties, coatingagents, grouting materials or mortar. This thermoplastic form may alsobe injection-molded, extruded or worked-up in a kneader.

In many cases, the poly(urethane silicate) resinous and foamed productsproduced by the invention are soluble in organic solvents and may beused as a tough coating agent for wood and metal. The mixtures of theinvention are also suitable for use as impregnating agents for finishingfibers. The mixtures may also be extruded through discs or slots andconverted into fibers and foils. These fibers and foils may be used forproducing synthetic incombustible paper or fleeces.

When the polyester silicate and polyisocyanate are combined withexpanded clay and an alkali metal silicate solution, a very goodconcrete is obtained which can, for example, be used as panels in theconstruction field. In this case, the foam material (expanded clay)plays the part of the binding material.

An additional step may be taken wherein up to 10 parts by weight of anepihalohydrin, selected from the group consisting of epichlorohydrin,epibromohydrin, epifluorohydrin and mixtures thereof; and alkalicatalyst, selected from the group consisting of sodium hydroxide,potassium hydroxide and mixtures thereof in an amount wherein the alkalimetal radicals are about equal to the halide radicals; and 10 to 30parts by weight of the polyester silicate resinous product of Claim 1are mixed and reacted in a closed system at a temperature below theboiling temperature of the reactants, thereby producing an epoxysilicate resinous product. Then up to 10 parts by weight of anepoxy-curing catalyst, selected from the group consisting of a Lewisacid and an amine, are mixed and reacted at ambient temperature andpressure, thereby producing an epoxy silicate product. In some cases, itis better to elevate the pressure up to 45 psi in the production ofepoxy silicate resinous products. The reaction time is 20 to 90 minutes.Epichlorohydrin is the preferred epihalohydrin.

The epoxy silicate resinous product may be cured by a catalyst such asamines, Lewis acids, alkali metal oxides or hydroxides, mercaptans,phenols, alcohols, aminosilicates with free amine groups, phenoplast,aminoplasts, phenoplast silicates, aminoplast silicates, polyamides,polyamide silicates and mixtures thereof. Up to 200 parts by weight ofan epoxy-curing catalyst may be used with 100 parts by weight of theepoxy silicate resinous product.

Any suitable Lewis acid may be used in this invention. A "Lewis acid" isdefined for the purpose of this invention as any electron-acceptingmaterial relative to the polymer to which it is complexed. Examples ofLewis acids are quinones, mineral acids, acid anhydrides, organicphosphonic acids, nitrophenols, metal halides, organic acids, and thelike. Polycarboxyl acids and/or polycarboxyl acid anhydrides are thepreferred Lewis acid.

Any suitable organic amine may be used as the epoxy-curing catalyst;however, polyamines are preferred. The alkylene polyamines are preferredwhich have the formula

    NH.sub.2 (RNH).sub.n H

wherein R is an alkylene radical or a hydrogen-substituted alkyleneradical, and n is an integer of at least one, there being no upper limitto the number of alkylene groups.

Other suitable polyamides which may be used in this invention includethose organic materials possessing a plurality of amino hydrogen, e.g.,a plurality of ##STR4## groups wherein N is an amino nitrogen. Theseinclude the aliphatic, cycloaliphatic, aromatic or heterocyclicpolyamines as well as derivatives thereof, as long as the derivativesstill contain the necessary amino hydrogen.

Diethylenetriamine is the preferred epoxy-curing catalyst.

Polyhydric alcohols may be used with the substituted organic monohydroxycompound. They may be saturated, unsaturated or substituted. Thepolyhydric alcohol may be added in an amount up to 10 parts by weight.

Suitable polyhydric alcohols include, but are not limited to, ethyleneglycol; propylene-1,2- and -1,3-glycol; butylene-1,4-and -2,3-glycol;hexane-1,6-diol; octane-1,8-diol; neopentyl glycol;cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);2-methyl-propane-1,3-diol; diethylene glycol; triethylene glycol;tetraethylene glycol; polyethylene glycols; dipropylene glycol;polypropylene glycols; dibutylene glycol and polybutylene glycols. Theunsaturated polyester resins may contain lactones such asε-caprolactone, or hydrocarboxylic acids such as ω-hydroxy-caproic acid.Polyethers containing 2 hydroxyl groups may be used in production ofunsaturated polyester resins and may be prepared, e.g., by thepolymerization of epoxides, e.g., ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styreneoxide or epichlorohydrin, eachwith itself, e.g., in the presence of BF₃, or by addition of theseepoxides, optionally as mixtures or successively, to starting componentssuch as alcohols or amines, e.g., water; ethylene glycol; propylene-1,3-or -1,2-glycol; trimethylol propane; 4,4'-dihydroxydiphenylpropane;aniline; ammonia; ethanolamine or ethylenediamine. The polyethers may bemodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitrile in the presence of polyethers.

Suitable unsaturated alcohols such as allyl alcohol may be reacted withdibasic acids such as phthalic anhydride, succinic acid, maleic acid,maleic anhydride, itaconic acid and fumaric acid to produce allyl esterswhich may be polymerized alone or with other polymerizing monomers.Allyl esters such as diethylene glycol bis(allyl carbonate), diallylmaleate, diallyl fumarate, diallyl phthalate, diallyl benzenephosphonate, allyl itaconate and methallyl methacrylate may be used inthis invention. Triallyl cyanurate may be reacted with unsaturatedpolyester resins to produce resins, and may be used as the polymerizingmonomer.

Other unsaturated alcohols may be reacted with dibasic acids; theseinclude other polymeric allyl-type alcohols which are alcohols having adouble bond of aliphatic character between two carbon atoms, one ofwhich is attached directly to a saturated carbon atoms, which, in turn,is attached directly to an alcoholic hydroxyl group, as represented bythe general structural formula

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specificExamples which follow, it being understood that these preferredembodiments are illustrative of, but not limited to, procedures whichmay be used in the production of polyester silicate resinous products.Parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

About 10 parts by weight of sodium metasilicate pentahydrate, about 30parts by weight of phthalic anhydride and 10 parts by weight of ethylenechlorohydrin are mixed, then heated to a temperature between the meltingpoint of phthalic acid and the boiling pont of ethylene chlorohydrinwhile agitating for 20 to 90 minutes. The temperature may then begradually increased, up to 250° C., until the desired viscosity isobtained, thereby producing a cream-colored polyester silicate resinousproduct.

About 3 parts by weight of the phthalic anhydride may be replaced with 5parts by weight of linseed oil for other polymerizable vegetable oils.

EXAMPLE 2

About 20 parts by weight of an aqueous solution of sodium silicate,containing 10 parts by weight of anhydrous sodium silicate, 30 parts byweight of phthalic acid and 15 parts by weight of ethylene chlorohydrinare mixed, then heated to a temperature between the melting temperatureof phthalic acid and the boiling temperature of ethylene chlorohydrinwhile agitating for 20 to 90 minutes. The temperature is then graduallyincreased, up to 250° C., while agitating until the desired viscosity isobtained, thereby producing a polyester silicate resinous product.

About 3 parts by weight of the phthalic acid may be replaced with about5 parts by weight of diethylene glycol bis (allyl carbonate).

EXAMPLE 3

About 10 parts by weight of potassium metasilicate pentahydrate, 5 partsby weight of phthalic anhydride, 15 parts by weight of maleic anhydride,and 10 parts by weight of ethylene chlorohydrin are mixed, then heatedto a temperature between the melting temperature of the polycarboxylacids and the boiling temperature of the ethylene chlorohydrin whileagitating for 20 to 90 minutes, thereby producing polyester silicateresinous product. The temperature is then gradually increased, up to250° C., while agitating until the desired viscosity is obtained. Theresinous product may be produced as a thick liquid or a hard solid.

The thick liquid (viscosity of 500 to 1,500 poises) is mixed withstyrene in the ratio of about 2 to 1 parts by weight. Then a catalyticamount of a peroxide initiator, methyl ethyl ketone peroxide (0.2 to 0.5part by weight), and an activator, cobalt naphthenate (30 to 100 ppm ofcobalt metal), are added and mixed at a temperature of 20° C. to 60° C.,thereby producing a hard, solid condensation product. The above solutionmay be applied to a fiberglass cloth to produce rigid sheets and may beused to build containers, roofing, etc.

EXAMPLE 4

About 10 parts by weight of sodium metasilicate pentahydrate, 15 partsby weight of glycerol, 10 parts by weight of ethylene chlorohydrin and30 parts by weight of phthalic anhydride are mixed, then heated to atemperature just below the boiling temperature of ethylene chlorohydrinfor 20 to 90 minutes while agitating at ambient pressure, therebyproducing a cream-colored polyester silicate resinous product.

A mineral acid, sulfuric acid, is then added slowly to the polyestersilicate resinous product in the amount wherein the sulfuric acid andunreacted alkali metal radicals are about equal, while agitating,thereby producing a polyester silicate resinous product. This product issoluble in common solvents such as acetic acid and the solution ofpolyester silicate may be painted on wood to produce a tough, protectivecoating when dried.

Other polycarboxylic acids may be used in place of phthalic anhydride,such as phthalic acid, maleic acid, maleic anhydride, succinic acid,succinic anhydride, glutaric anhydride, glutaric acid, poly(adipicanhydride), adipic acid, tetrachlorophthalic anhydride, diglycolicanhydride, fumaric acid, azelaic acid, sebacic acid, terephthalic acid,oxalic acid, itaconic acid, nitrophthalic acid anhydride, pyromelliticanhydride, tetrahydrophthalic anhydride, dodecenylsuccinic anhydride,hexadecylsuccinic anhydride and mixtures thereof.

EXAMPLE 5

About 20 parts by weight of the polyester silicate resinous product, asproduced in Example 1, 10 parts by weight of polypropylene glycol (mol.wt. 1200) and 20 parts by weight of "crude MDI" are mixed, then 1 partby weight of triethylenediamine is admixed thoroughly and the mixtureexpands 8 to 15 times its original volume, thereby producing a tough,semi-rigid polyurethane silicate foam with excellent fire-retardantproperties.

Other polyols (polyhydroxyl organic compounds) may be used in place ofpolypropylene glycol, such as polyesters, polyethers, polyamides,polythioethers, polyacetals, polybutadiene, phenoplast and aminoplastscontaining 2 or more hydroxyl radicals, castor oil, carbohydrates,cellulose, modified polyethers with vinyl compounds, and mixturesthereof.

EXAMPLE 6

About 20 parts by weight of the polyester silicate resinous product, asproduced in Example 2, 4 parts by weight of trichlorotrifluoroethane,0.5 part by weight of triethylenediamine and 15 parts by weight of apolyurethane prepolymer, as listed below, are thoroughly mixed at atemperature between ambient temperature and 45° C. The mixture expands 3to 15 times its original volume, producing a rigid polyurethane silicatefoam which has excellent flame-retardant and insulation properties. Thefoam may be used for packaging and for sound and thermal insulation.

    ______________________________________    Example  Polyurethane prepolymer    ______________________________________    a        Toluene diisocyanate with polypropylene glycol             (mol. wt. 500) in an NCO/OH ratio of 25:1.    b        Diisocyanatodiphenylmethane with a tetrafunc-             tional polypropylene glycol (mol. wt. 500)             to produce a prepolymer having about 22%             NCO groups.    c        Methylene bis-phenyl diisocyanate with a liquid             polyepichlorohydrin to produce a prepolymer             of NCO of about 16% and containing 25% by             weight of a resin extender, polyalpha-methyl             styrene.    d        Toluene diisocyanate with castor oil to produce             a prepolymer with an NCO content of about 15%.    ______________________________________

EXAMPLE 7

About 10 parts by weight of sodium metasilicate, 5 parts by weight ofglycerol, 5 parts by weight of linseed oil, 10 parts by weight ofethylene chlorohydrin, 5 parts by weight of sebacic acid and 20 parts byweight of phthalic anhydride are mixed in a container which is equippedwith a reflux condenser, agitator, sparger, a foam breaker and hassuitable means for sampling and discharge. The reaction may be carriedout in an inert atmosphere, usually carbon dioxide or nitrogen. A vacuummay be applied to the reactor to remove the water. The mixture is heatedto 100° C. to 250° C. while agitating for 20 to 90 minutes, therebyproducing a polyester silicate resinous product.

EXAMPLE 8

About 10 parts by weight of sodium metasilicate pentahydrate, 10 partsby weight of ethylene chlorohydrin, 10 parts by weight of glycerol and20 parts by weight of adipic acid are mixed, then heated to atemperature between the melting point of adipic acid and the boilingtemperature of the components while agitating for 20 to 90 minutes,thereby producing a thick liquid polyester silicate resinous product.

About equal parts by weight of the polyester silicate resinous productand a polyisocyanate, as listed below, and 5% by weight of triethylamineare mixed at 30° C. to 45° C., then thoroughly agitated until themixture begins to expand, thereby producing a rigid polyurethanesilicate foam.

    ______________________________________    Example           Polyisocyanate    ______________________________________    a      Tolylene diisocyanate.    b      Tolylene diisocyanate ("TDI" produced by Olin           Chemical).    c      "MDI" (polyphenyl-polymethylene-isocyanate).    d      "PAPI 27" produced by Upjohn Co. (a polyphenyl-           polymethylene-isocyanate).    e      "Crude MDI" (a polyphenyl-polymethylene-iso-           cyanate).    f      20% solution of "TDI" residue in "crude MDI"           with NCO content of about 30%.    g      Isocyanate-terminated reaction product of MDI           with polyethylene glycol containing about           24% NCO.    h      A solution containing 80% "crude MDI" and 20%           "TDI".    i      4,4-diphenylmethane diisocyanate.    j      Sulphonated polyphenyl-polymethylene poly-           isocyanate, sulfur content of about 1%           and NCO content of about 30%.    k      Tolylene diisocyanate silicate prepolymer           (100 parts by weight of "TDI" with 10           parts by weight of hydrated silica).    l      Sodium silicate-tolylene diisocyanate pre-           polymer (100 parts by weight of "TDI"           with 20 parts by weight of sodium meta-           silicate).    ______________________________________

EXAMPLE 9

About 10 parts by weight of the polyester silicate produced in Example3, 5 parts by weight of an amine polyether sucrose (POLY G 71-357produced by Olin), 5 parts by weight of methylene chloride, 15 parts byweight of "MDI" (polyphenylpolymethylene-isocyanate), 30 parts by weightof fine sand and 30 parts by weight of Portland cement are mixedthoroughly, then poured into a mold, such as a cement block mold, wherethe mixture expands 5 to 15 times its original volume and hardens within5 minutes to produce a hard, rigid polyurethane silicate resinousproduct. After the product has hardened, it is then placed in water towet the product thoroughly in order to cure any unreacted cement. Theproduct has excellent flame-retardant properties and is a fine sound andthermal insulator.

Other water-binding agents may be used in place of Portland cement suchas other hydraulic cements, synthetic anhydrides, gypsum, burnt lime andmixtures thereof.

EXAMPLE 10

About 30 parts by weight of the polyester silicate, as produced inExample 3, 10 parts by weight of methyl methacrylate, 0.2 to 0.5 part byweight of methyl ethyl ketone peroxide and sufficient cobalt naphthanateto produce 100 ppm are mixed at ambient pressure and at a temperaturebetween 20° C. and 60° C., thereby producing a tough, solid polyestersilicate resinous product.

EXAMPLE 11

About 30 parts by weight of the polyester silicate, as produced inExample 3, 10 parts by weight of styrene, 0.2 to 0.5 part by weight ofmethyl ethyl ketone, sufficient cobalt naphthanate to produce 100 ppm,0.2 part by weight of a solution containing equal parts by weight oftriethylenediamine and ethanolamine, 5 parts by weight oftrichlorotrifluoroethane and 20 parts by weight of "crude MDI" arethoroughly mixed at ambient temperature up to 35° C. The mixture expandsin a few seconds to 5 to 15 times its original volume, thereby producinga tough, rigid polyurethane silicate foam.

EXAMPLE 12

About 100 parts by weight of the polyester silicate resinous productproduced in Example 3, 20 parts by weight of methyl methacrylate and 20parts by weight of vinyl toluene are mixed, thereby forming a solution;then 0.2 to 0.5 part by weight of benzoyl peroxide, 0.5 part by weightof potassium persulfate, 0.001 part by weight of cupric sulfate, 0.01part by weight of diethyl aniline, 20 parts by weight of methylenechloride, 300 parts by weight of Portland cement and 75 parts by weightof water are thoroughly mixed, then poured into a closed mold at atemperature just above the boiling temperature of methylene chloride.The mixture cures in 1 to 12 hours, thereby producing a foamed polyestersilicate concrete product.

The foamed polyester silicate concrete product may be utilized forthermal and sound insulation, construction components, art objects, etc.

Other water-binding components may be used in place of Portland cement,such as other hydraulic cements, gypsum, burnt lime and syntheticanhydrite.

EXAMPLE 13

About 10 parts by weight of sodium metasilicate pentahydrate, 15 partsby weight of ethylene chlorohydrin, 15 parts by weight of phthalicanhydride and 5 parts by weight of linseed oil are mixed, then heated toa temperature between the melting point of phthalic anhydride and theboiling temperature of ethylene chlorohydrin while agitating for 20 to90 minutes, thereby producing a polyester silicate resinous product.

The polyester silicate resinous product is soluble in organic solventsand may be used as a coating agent for wood or metal.

Other vegetable oils may be used in place of linseed oil, such ascottonseed oil, tung oil, fish oil, perilla oil, oiticica oil, sunfloweroil, safflower oil, walnut oil, dehydrated castor oil, monoglyceride ofvegetable oils and mixtures thereof.

EXAMPLE 14

About 100 parts by weight of the polyester silicate resinous product asproduced in Example 3 and 30 parts by weight of styrene are mixed,thereby forming a solution, then 10 parts by weight oftrichlorotrifluoroethane, 0.5 part by weight of a water-solublepolyester siloxane, 0.2 to 0.5 part by weight of methyl ethyl ketoneperoxide, and sufficient cobalt naphthanate to produce about 100 ppm ofcobalt in the mixture are added, thoroughly mixed and poured into aclosed mold which has a temperature between 70° C. to 90° C. The mixtureis cured in 30 minutes to 12 hours, thereby producing a foamed polyestersilicate product.

The foamed polyester silicate product may be used for thermal and soundinsulation.

EXAMPLE 15

About 100 parts by weight of the polyester silicate resinous productproduced in Example 3, 20 parts by weight of styrene and 10 parts byweight of vinyl acetate are mixed, thereby forming a solution, then 0.2to 0.5 part by weight of benzoyl peroxide, 0.01 part by weight ofdiethyl aniline, 200 parts by weight of Portland cement and 50 parts byweight of water are thoroughly mixed, then applied to layers offiberglas to produce a polyester silicate concrete panel which cures in1 to 12 hours. The panel may be used in construction, boat building,packaging, etc.

Other water-binding agents may be used in place of Portland cement, suchas other hydraulic cements, gypsum, burnt lime and synthetic anhydrites.

EXAMPLE 16

About 10 parts by weight of fine granular sodium silicate (Na₂ O:SiO₂ratio of 1:2), 10 parts by weight of ethylene chlorohydrin, 5 parts byweight of glycerol, 15 parts by weight of phthalic anhydride and 5 partsby weight of adipic acid are mixed, then heated to a temperature betweenthe melting temperature of phthalic anhydride and the boilingtemperature of ethylene chlorohydrin while agitating at ambient pressurefor 20 to 90 minutes, thereby producing a polyester silicate resinousproduct and salt.

Other polyhydroxy organic compounds (polyols) may be used in place ofglycerol, such as ethylene glycol, propylene glycol diethylene etherglycol, butylene glycol, trimethylol propane, and mixtures thereof.

Other halohydrins may be used in place of ethylene chlorohydrin, such asethylene bromohydrin, glycerol monochlorohydrin and mixtures thereof.

EXAMPLE 17

About 10 parts by weight of sodium silicate powder (Na₂ O:SiO₂ ratio of1:2), 10 parts by weight of 2-nitro-1-hydroxy propane, 5 parts by weightof glycerol, 10 parts by weight of phthalic anhydride and 5 parts byweight of dehydrated castor oil are mixed, then heated to a temperaturejust below the boiling temperature of 2-nitro-1-hydroxy propane whileagitating at ambient pressure for 20 to 90 minutes, thereby producing apolyester silicate resinous product.

EXAMPLE 18

About 20 parts by weight of the polyester silicate resinous product asproduced in Example 17, 5 parts by weight of epichlorohydrin and 3 partsby weight of caustic soda are mixed, then heated to a temperature justbelow the boiling temperature of epichlorohydrin while agitating atambient pressure in a closed system for 20 to 90 minutes, therebyproducing an epoxy silicate resinous product. About 100 parts by weightof the epoxy silicate resinous product are mixed with 20 parts by weightof diethylenetriamine and thoroughly mixed, then applied to fiberglas.The mixture hardens within 12 hours to produce a hard, tough epoxysilicate product which may be used as construction panels, to produceboats, etc.

Although specific materials and conditions were set forth in the aboveexamples, these were merely illustrative of preferred embodiments of myinvention. Various other compositions, such as the typical materialslisted above, may be used where suitable. The reactive mixtures andproducts of my invention may have other agents added thereto to enhanceor otherwise modify the reaction and products.

Other modifications of my invention will occur to those skilled in theart upon reading my disclosure. These are intended to be included withinthe scope of my invention, as defined in the appended Claims.

I claim:
 1. The process for the production of polyester silicateresinous product by mixing and reacting the following components:(A) analkali metal silicate, 1 to 10 parts by weight; (B) an organicmonohydroxy compound having a substituent which will split off duringthe reaction and the substituent radical is selected from the groupconsisting of halogen, acid sulfate, nitrate, acid phosphate,bicarbonate, sulfate, formate, acetate, propionate, laurate, oleate,stearate, and mixtures thereof, (C) a polycarboxylic acid and/orpolycarboxylic acid anhydride, 10 to 30 parts by weight.
 2. The processof claim 1 wherein the alkali metal silicate is selected from the groupconsisting of sodium silicate, potassium silicate, lithium silicate andmixtures thereof.
 3. The process of claim 1 wherein the alkali metalsilicate is sodium silicate.
 4. The process of claim 1 wherein thesubstituted organic monohydroxy compound is an organic halohydrin. 5.The process of claim 1 wherein the substituted organic monohydroxycompound is ethylene chlorohydrin.
 6. The process of claim 1 wherein upto 10 parts by weight of a polyhydric alcohol is mixed and reacted withcomponents A, B and C.
 7. The process of claim 6 wherein the polyhydricalcohol is selected from the group consisting of ethylene glycol,propylene glycol, butylene glycol, trimethylene glycol, tetramethyleneglycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol,polyethylene glycol, polypropylene glycol, bis(β-hydroxyethyl)terephthalate, Bisphenol A, resorcinol, glycerol, glycerolmonochlorohydrin, trimethol ethane, and carbohydrates.
 8. The process ofclaim 1 wherein the polycarboxylic acid is selected from the groupconsisting of maleic acid, phthalic acid, succinic acid, oxalic acid,malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,isophthalic acid, fumaric acid, azelaic acid, sebacic acid, terephthalicacid, itaconic acid, diglycolic acid, tartaric acid, and mixturesthereof.
 9. The process according to claim 1 wherein up to 5 parts byweight of the polycarboxylic acid and/or polycarboxylic acid anhydrideis replaced with a polymerizable oil, selected from the group consistingof soybean oil, linseed oil, cottonseed oil, tung oil, fish oil, perillaoil, oiticica oil, sunflower oil, safflower oil, walnut oil, dehydratedcastor oil, monoglyceride of vegetable oils and mixtures thereof. 10.The process according to claim 1 wherein up to 5 parts by weight of thepolycarboxylic acid and/or polycarboxylic acid anhydride is replacedwith a linear organic carbonate selected from the group consisting ofp-xylene glycol bis(ethyl carbonate), diethylene glycol bis(allylcarbonate) and mixtures thereof.
 11. The process according to claim 1wherein up to 5 parts by weight of the organic monohydroxy compoundhaving a substituent which will split off during the reaction andpolycarboxylic acid is replaced with an organic compound containinghydroxyl and carboxylic radicals, selected from the group consisting of10-hydroxyl undecanoic acid, 2 hydroxy decanoic acid,ω-hydroxypentadecanoic acid and mixtures thereof.
 12. The productproduced by the process of claim
 1. 13. The product produced by theprocess of claim
 7. 14. The product produced by the process of claim 9.15. The product produced by the process of claim
 10. 16. The productproduced by the process of claim
 11. 17. The process according to claim1, wherein an additional step is taken wherein a catalytic amount of aperoxide initiator selected from the group consisting of acetyl benzoylperoxide, peracetic acid methyl ethyl ketone peroxide, cyclohexanoneperoxide, cyclohexyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, cumenehydroperoxide, tert-butyl hydroperoxide, methyl amyl ketone peroxide,lauroyl peroxide, benzoyl peroxide, tert-butyl perbenzoate,p-chlorobenzoyl peroxide, dibenzal diperoxide and mixtures thereof isadmixed with the polyester silicate resinous product.